US4293718A - Preparation of acetaldehyde - Google Patents

Preparation of acetaldehyde Download PDF

Info

Publication number
US4293718A
US4293718A US06/087,631 US8763179A US4293718A US 4293718 A US4293718 A US 4293718A US 8763179 A US8763179 A US 8763179A US 4293718 A US4293718 A US 4293718A
Authority
US
United States
Prior art keywords
gram
iodide
cobalt
halogen
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US06/087,631
Other languages
English (en)
Inventor
Jean Gauthier-Lafaye
Robert Perron
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhone Poulenc Industries SA
Original Assignee
Rhone Poulenc Industries SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=9214627&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US4293718(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Rhone Poulenc Industries SA filed Critical Rhone Poulenc Industries SA
Application granted granted Critical
Publication of US4293718A publication Critical patent/US4293718A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide

Definitions

  • the present invention relates to a process for the preparation of acetaldehyde.
  • the process comprises the carbonylation of methanol in the presence of hydrogen.
  • this invention relates to a process for the preparation of acetaldehyde which comprises reacting methanol with a mixture of CO and H 2 in the presence of cobalt, a halogen-containing promoter and an ionic iodide.
  • Acetaldehyde is an intermediate of great value in the chemical industry. It is useful, in particular, for the manufacture of acetic acid and acetic anhydride, e.g., see the Encyclopedia of Chemical Technology, Kirk-Othmer, 3rd Edition, Volume 1, pages 97 et seq.
  • U.S. Pat. No. 3,356,734 discloses that the presence of an amount of cobalt less than 2 millimols of cobalt per mol of methanol in a cobalt-halogen catalyst system favors the conversion of methanol to acetaldehyde.
  • the carbonylation of methanol is carried out with a CO/H 2 molar ratio of 1.4 for 2 hours at 185° C. under a pressure of 300 to 400 atmospheres employing the technique disclosed in U.S. Pat. No. 3,356,734
  • about 130 g of acetaldehyde are obtained per liter of reaction medium per hour. This is a productivity on the order of 70 g of acetaldehyde per hour per gram of cobalt employed in the reaction, taking into account the fact that the dimethoxyethane formed is a potential source of acetaldehyde.
  • a major object of the present invention is the provision of a novel process for the selective carbonylation of methanol, affording yields of acetaldehyde heretofore unavailable to this art, and which novel process is conspicuously devoid of those disadvantages and drawbacks which heretofore have characterized the prior art process.
  • Another object of this invention is to provide a process for producing acetaldehyde by the carbonylation of methanol which converts little or none of the methanol to butanol, butanal, or butenal.
  • Another object of the present invention is to provide a process for the carbonylation of methanol in the presence of hydrogen and cobalt which considerably increases the productivity per hour of acetaldehyde relative to the amount of cobalt employed in the reaction, virtually without loss of productivity relative to the reaction volume.
  • the ratio of the gram-ions of I - , originating from the ionic iodide, to the number of gram-atoms of cobalt employed is at least 5; and, the number of gram-atoms of halogen originating from the halogen-containing promoter represent from about 0.1 to about 10% of the number of gram-ions of I - .
  • ionic iodide is to be understood as meaning any inorganic or organic iodide, taken either alone or in admixture, the cation of which is selected from the group consisting of alkali metal cations, alkaline earth metal cations, ammonium and quaternary ammonium cations and phosphonium and quaternary phosphonium cations. The precise nature of the ammonium and phosphonium cation is not of critical importance.
  • a suitable cation is further governed, however, by considerations of a practical nature, such as the solubility, availability and convenience of using the particular ionic iodide.
  • suitable compounds are the quaternary ammonium iodides derived from lower trialkylamines, (e.g., trimethylamine, and tributylamine), alkylarylamines (such as dimethylaniline), cyclic tertiary amines (such as N-alkylpyrrolidines or piperidines), N-alkylhexamethyleneimines, pyrrole, pyridine or alkylpyridines which are quaternized by treatment with esters of hydriodic acid and aliphatic alcohols.
  • Bis-quaternary ammonium iodides which are derived, for example, from tetraalkylalkylenediamines, are also within the scope of the present invention.
  • Suitable phosphonium iodides for purposes of this invention are those derived from triarylphosphines and trialkylphosphines, preferably those which are readily available, e.g., triphenylphosphine, tritolylphosphine, trixylylphosphine, trimethylphosphine, tributylphosphine and tricyclohexylphosphine, which are quaternized by alkyl or aralkyl iodides.
  • Bis-quaternary phosphonium iodides derived, for example, from bis- ⁇ , ⁇ -(diphenylphosphino)alkanes, are also suitable for purposes of the present invention.
  • a preferred embodiment of the present invention comprises the use of alkali metal or alkaline earth metal iodides, e.g., LiI, NaI, KI, CsI and CaI 2 .
  • alkali metal or alkaline earth metal iodides e.g., LiI, NaI, KI, CsI and CaI 2 .
  • the use of one or more alkali metal iodide is preferred with the use of NaI or KI being most preferred.
  • the ratio of gram-ions of I - to gram-atoms of Co (I - /Co), with I - originating from the ionic iodide, is preferably equal to at least 5. Although this ratio can vary within wide limits, it does not seem to be advantageous to exceed a value of 200. In a specific embodiment of this invention, the ratio (I - /Co) is greater than or equal to 10. It is particularly advantageous for the ratio I - /Co to be greater than or equal to 20.
  • halogen-containing promoter is to be understood as meaning any compound formed by replacing at least one hydrogen atom of an organic molecule which only contains carbon and hydrogen with a halogen, e.g., hydrocarbyl chlorides, bromides, and most preferably iodides, or, any compound which, under the reaction conditions, is capable of leading to the production of a methyl halide in the reaction medium, in particular; Cl 2 , Br 2 , I 2 , HCl, HBr, HI, CoBr 2 and CoI 2 .
  • the lower alkyl chlorides bromides and iodides having from 1 to 4 carbon atoms in the molecule.
  • examples are methyl bromide and iodide and ethyl bromide and iodide.
  • halogen-containing promoter is appreciable, even in minor proportions, e.g., proportions on the order of 0.1 gram-atom of halogen (denoted as " ⁇ " in the description which follows) per 100 gram-ions of iodide, i.e., a ratio of X/I - on the order of 0.001. It is not desirable to exceed a value of 0.1 for this ratio, however, particularly to limit the corrosion of the apparatus, but also for technological reasons.
  • the process is preferably carried out with a ratio of X/I - in the range of about 0.01 to about 0.08.
  • the process according to this invention is also carried out in the presence of cobalt.
  • Any source of cobalt which will react with carbon monoxide in the reaction medium to provide a cobalt carbonyl, cobalt carbonyl hydride or a cobalt carbonylate complex can be used for purposes of the present invention.
  • Typical sources of cobalt are, for example, finely divided cobalt metal, inorganic salts such as cobalt carbonate and organic salts, in particular, fatty acid salts.
  • Cobalt carbonyls and cobalt carbonyl hydrides, or, the complexes thereof, can also be employed.
  • Cobalt acetate, cobalt formate, cobalt halides, particularly cobalt iodide, and dicobalt octacarbonyl are among the cobalt derivatives which are suitable for carrying out the process of the present invention.
  • the process is carried out with a catalytically effective amount of cobalt.
  • An effective amount of cobalt is that quantity sufficient to obtain the reaction rate and results desired.
  • an effective amount is such an amount that the ratio of the number of milligram-atoms of cobalt to the number of mols of methanol (Co/CH 3 OH) is in the range of about 0.01 to about 1 and preferably in the range of about 0.05 to 0.4.
  • the carbonylation process according to the present invention is preferably carried out in the liquid phase. Since it is preferred to carry out the process with excess methanol, the simultaneous use of an additional solvent is generally superfluous, but, in principle, such inert organic solvents as hydrocarbons, esters, ethers and the reaction products, can be used.
  • the methanol employed as technical-grade methanol can be used.
  • the methanol used can contain up to 50% water and/or methyl acetate.
  • the halogen-containing promoters, the ionic iodides and the cobalt-based compounds used can also be of technical grade.
  • a mixture of carbon monoxide and hydrogen is reacted with methanol. It is essential that the mixture contain at least 25 mol% hydrogen. In general, mixtures containing up to 95% hydrogen can be used. The use of mixtures containing from 40 to 80% of hydrogen are preferred.
  • the mixture of gases can contain impurities such as carbon dioxide, oxygen, methane and nitrogen.
  • the reaction is generally run with a total pressure in the range of about 50 to about 600 bars.
  • the total pressure is preferably between 75 and 350 bars and most preferably between 100 and 320 bars.
  • the reaction temperature employed be at least about 165° C.
  • the temperature can reach 240° C. if the reaction is conducted without a solvent. If a solvent is employed, this being optional within the scope of the present invention, the temperature can be as high as about 300° C.
  • the reaction temperature preferably is within the range of about 180° C. to about 230° C.
  • EtOH denotes ethanol
  • C 4 denotes all the products formed which have 4 carbon atoms in the molecule, particularly butenal, butanal and butanol.
  • MeOMe denotes dimethyl ether (which product can be recycled to the reaction).
  • RR for a given product, is equal to the ratio of the number of mols of the product formed during the reaction to the number of mols of methanol employed in the reaction. Exceptions are RR(C 4 ) and RR (MeOMe), which are equal to twice the ratio defined above.
  • ⁇ RR is the sum of the RR values defined above for all the products with the exception of dimethyl ether. N.B. In all the examples below, ##EQU1## is less than 0.01.
  • a first series of control experiments (a, b and c) was carried out in accordance with the analogous procedure described below for control experiment b.
  • ⁇ RR was equal to 19% and virtually no C 4 was observed (RR/ ⁇ RR ⁇ 1%).
  • ⁇ RR was equal to 15.2% and virtually no C 4 was observed.
  • ⁇ RR was equal to 14.5% and virtually no C 4 was observed.
  • ⁇ RR was equal to 18.6% and virtually no C 4 was observed.
  • ⁇ RR was equal to 12.3% and virtually no C 4 was observed.
  • ⁇ RR was equal to 6.9% and virtually no C 4 was observed.
  • ⁇ RR was equal to 16.7% and virtually no C 4 was observed.
  • ⁇ RR was equal to 9.4% and virtually no C 4 was observed.
  • ⁇ RR was equal to 12.7% and virtually no C 4 was observed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Saccharide Compounds (AREA)
US06/087,631 1978-10-31 1979-10-23 Preparation of acetaldehyde Expired - Lifetime US4293718A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7831634A FR2441603A1 (fr) 1978-10-31 1978-10-31 Procede de preparation de l'acetaldehyde
FR7831634 1978-10-31

Publications (1)

Publication Number Publication Date
US4293718A true US4293718A (en) 1981-10-06

Family

ID=9214627

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/087,631 Expired - Lifetime US4293718A (en) 1978-10-31 1979-10-23 Preparation of acetaldehyde

Country Status (10)

Country Link
US (1) US4293718A (enrdf_load_stackoverflow)
EP (1) EP0011042B2 (enrdf_load_stackoverflow)
JP (1) JPS5564539A (enrdf_load_stackoverflow)
AT (1) ATE199T1 (enrdf_load_stackoverflow)
BR (1) BR7907034A (enrdf_load_stackoverflow)
CA (1) CA1125311A (enrdf_load_stackoverflow)
DD (1) DD146943A5 (enrdf_load_stackoverflow)
DE (1) DE2960788D1 (enrdf_load_stackoverflow)
ES (1) ES485527A1 (enrdf_load_stackoverflow)
FR (1) FR2441603A1 (enrdf_load_stackoverflow)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4361707A (en) * 1981-08-03 1982-11-30 Gulf Research & Development Company Process for producing aldehydes
US4361706A (en) * 1981-08-03 1982-11-30 Gulf Research & Development Company Process for preparing aldehydes
US4400551A (en) * 1980-08-21 1983-08-23 Union Rheinische Braunkohlen Kraftstoff Aktiengesellschaft Process for the production of acetaldehyde and ethanol
US4408080A (en) * 1980-06-18 1983-10-04 Mitsubishi Gas Chemical Company, Inc. Process for producing acetaldehyde
US4556744A (en) * 1983-10-08 1985-12-03 The British Petroleum Company P.L.C. Process for the production of ethanol and/or acetaldehyde by the metal catalysed liquid phase reaction of methanol, carbon monoxide and hydrogen in the presence of a solvent
US20050154239A1 (en) * 2004-01-08 2005-07-14 Windhorst Kenneth A. Methods for preparing 1,3 butylene glycol
US9238606B1 (en) 2014-12-30 2016-01-19 Eastman Chemical Company Methyl-Iodide-free carbonylation of methanol to acetaldehyde
US9266806B1 (en) 2014-12-30 2016-02-23 Eastman Chemical Company Reductive carbonylation of methanol to acetaldehyde
US9266807B1 (en) 2014-12-30 2016-02-23 Eastman Chemical Company Conversion of alcohols to longer chain aldehydes or alcohols
US9365479B1 (en) 2014-12-30 2016-06-14 Eastman Chemical Company Methyl-iodide-free carbonylation of an alcohol to its homologous aldehyde and/or alcohol
US9714206B2 (en) 2014-12-30 2017-07-25 Eastman Chemical Company Methyl-iodide-free carbonylation of an alcohol to its homologous aldehyde and/or alcohol

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2460284A1 (fr) * 1979-07-04 1981-01-23 Rhone Poulenc Ind Procede de preparation de l'acetaldehyde
US4320230A (en) * 1979-09-24 1982-03-16 Exxon Research & Engineering Co. Methanol homologation using iron-cobalt carbonyl cluster catalyst
CA1155458A (en) * 1980-04-09 1983-10-18 Union Carbide Corporation Process for the selective hydroformylation of methanol to acetaldehyde
EP0098689B1 (en) * 1982-06-05 1986-12-17 BP Chemicals Limited Process for the production of monocarboxylic acid anhydrides
JPS6084239A (ja) * 1983-10-14 1985-05-13 Agency Of Ind Science & Technol アセトアルデヒドの製造法
DE3343519A1 (de) * 1983-12-01 1985-06-13 Union Rheinische Braunkohlen Kraftstoff AG, 5000 Köln Selektive herstellung von acetaldehyd
DE3506714A1 (de) * 1985-02-26 1986-08-28 Union Rheinische Braunkohlen Kraftstoff AG, 5000 Köln Verfahren zur kontinuierlichen homologisierung von methanol
JPH0374007U (enrdf_load_stackoverflow) * 1989-11-15 1991-07-25

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3248432A (en) * 1961-12-12 1966-04-26 Commercial Solvents Corp Process for the production of ethyl alcohol
US3285948A (en) * 1965-01-22 1966-11-15 Commercial Solvents Corp Halides of ruthenium and osmium in conjunction with cobalt and iodine in the production of ethanol from methanol
US3356734A (en) * 1963-02-28 1967-12-05 Kuraishi Michio Process for the production of acetaldehyde
JPS52133914A (en) * 1976-04-30 1977-11-09 Mitsubishi Gas Chem Co Inc Preparation of acetaldehyde
JPS52136111A (en) * 1976-05-10 1977-11-14 Mitsubishi Gas Chem Co Inc Preparation of acetaldehyde
US4151208A (en) * 1977-12-23 1979-04-24 Gulf Research & Development Company Process for the selective preparation of acetaldehyde from methanol and synthesis gas
GB1546428A (en) * 1975-06-09 1979-05-23 Shell Int Research Production of ethanol from methanol carbon monoxide and hydrogen

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3248432A (en) * 1961-12-12 1966-04-26 Commercial Solvents Corp Process for the production of ethyl alcohol
US3356734A (en) * 1963-02-28 1967-12-05 Kuraishi Michio Process for the production of acetaldehyde
US3285948A (en) * 1965-01-22 1966-11-15 Commercial Solvents Corp Halides of ruthenium and osmium in conjunction with cobalt and iodine in the production of ethanol from methanol
GB1546428A (en) * 1975-06-09 1979-05-23 Shell Int Research Production of ethanol from methanol carbon monoxide and hydrogen
JPS52133914A (en) * 1976-04-30 1977-11-09 Mitsubishi Gas Chem Co Inc Preparation of acetaldehyde
JPS52136111A (en) * 1976-05-10 1977-11-14 Mitsubishi Gas Chem Co Inc Preparation of acetaldehyde
US4151208A (en) * 1977-12-23 1979-04-24 Gulf Research & Development Company Process for the selective preparation of acetaldehyde from methanol and synthesis gas

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4408080A (en) * 1980-06-18 1983-10-04 Mitsubishi Gas Chemical Company, Inc. Process for producing acetaldehyde
US4400551A (en) * 1980-08-21 1983-08-23 Union Rheinische Braunkohlen Kraftstoff Aktiengesellschaft Process for the production of acetaldehyde and ethanol
US4361707A (en) * 1981-08-03 1982-11-30 Gulf Research & Development Company Process for producing aldehydes
US4361706A (en) * 1981-08-03 1982-11-30 Gulf Research & Development Company Process for preparing aldehydes
US4556744A (en) * 1983-10-08 1985-12-03 The British Petroleum Company P.L.C. Process for the production of ethanol and/or acetaldehyde by the metal catalysed liquid phase reaction of methanol, carbon monoxide and hydrogen in the presence of a solvent
US20050154239A1 (en) * 2004-01-08 2005-07-14 Windhorst Kenneth A. Methods for preparing 1,3 butylene glycol
US9238606B1 (en) 2014-12-30 2016-01-19 Eastman Chemical Company Methyl-Iodide-free carbonylation of methanol to acetaldehyde
US9266806B1 (en) 2014-12-30 2016-02-23 Eastman Chemical Company Reductive carbonylation of methanol to acetaldehyde
US9266807B1 (en) 2014-12-30 2016-02-23 Eastman Chemical Company Conversion of alcohols to longer chain aldehydes or alcohols
US9365479B1 (en) 2014-12-30 2016-06-14 Eastman Chemical Company Methyl-iodide-free carbonylation of an alcohol to its homologous aldehyde and/or alcohol
US9714206B2 (en) 2014-12-30 2017-07-25 Eastman Chemical Company Methyl-iodide-free carbonylation of an alcohol to its homologous aldehyde and/or alcohol
US9718754B2 (en) 2014-12-30 2017-08-01 Eastman Chemical Company Methyl-iodide-free carbonylation of an alcohol to its homologous aldehyde and/or alcohol

Also Published As

Publication number Publication date
DD146943A5 (de) 1981-03-11
ATE199T1 (de) 1981-09-15
FR2441603B1 (enrdf_load_stackoverflow) 1981-05-29
CA1125311A (fr) 1982-06-08
DE2960788D1 (en) 1981-11-26
EP0011042B2 (fr) 1986-03-26
ES485527A1 (es) 1980-05-16
FR2441603A1 (fr) 1980-06-13
EP0011042A1 (fr) 1980-05-14
JPS6344135B2 (enrdf_load_stackoverflow) 1988-09-02
EP0011042B1 (fr) 1981-09-09
BR7907034A (pt) 1980-07-15
JPS5564539A (en) 1980-05-15

Similar Documents

Publication Publication Date Title
US4293718A (en) Preparation of acetaldehyde
US4133966A (en) Selective formation of ethanol from methanol, hydrogen and carbon monoxide
US3769329A (en) Production of carboxylic acids and esters
US3772380A (en) Production of carboxylic acids and esters
US4328375A (en) Process for the production of ethanol and/or acetaldehyde in the presence of metal complex catalyst systems
US4189441A (en) Process for preparing esters from ethers or esters of lower homologous alcohols
US4239924A (en) Ethanol from methanol
US4002678A (en) Preparation of carboxylic acid anhydrides
US4306091A (en) Process for the preparation of acetaldehyde
US4335059A (en) Preparation of carboxylic acid anhydrides
US4251458A (en) Process for preparing carboxylic acid anhydrides
US4346020A (en) Novel catalyst system and process for producing ethanol using said novel catalyst system
US4389532A (en) Process for the preparation of acetaldehyde
EP0037586A1 (en) Process for the selective hydroformylation of methanol to acetaldehyde
JPS6323978B2 (enrdf_load_stackoverflow)
US5710325A (en) Manufacture of adipic acid
US4483804A (en) Preparation of carboxylic acid anhydrides
US4519956A (en) Process for selectively preparing acetic anhydride by carbonylation of methyl acetate in the presence of an iodide-free catalyst system
EP0146291B1 (en) Process for the production of carboxylic acids and/or esters thereof
JPH0338259B2 (enrdf_load_stackoverflow)
US4408080A (en) Process for producing acetaldehyde
CA1192226A (en) Process for preparing ethylene glycol and lower monohydric alcohols from syngas using a novel catalyst system
US4351953A (en) Preparation of carboxylic acids by carbonylation of alcohols
EP0173170B1 (en) Process for the preparation of anhydrous carboxylic acids from alcohols
US4436889A (en) Preparation of carboxylic acids by carbonylation of alcohols

Legal Events

Date Code Title Description
STCF Information on status: patent grant

Free format text: PATENTED CASE